395

Sustain. Environ. Res., 22(6), 395-400 (2012)

Hydrocracking of oil residue from palm oil mill effluent to biofuel

Hasanudin,1,* Muhammad Said,2 Muhammad Faizal,2 Muhammad Hatta Dahlan2 and
Karna Wijaya3
1

Department of Chemistry
Sriwijaya University
Palembang 30662, Indonesia
2
Department of Chemical Engineering
Sriwijaya University
Palembang 30662, Indonesia
3
Department of Chemistry
Gadjah Mada University
Yogyakarta 55281, Indonesia

Key Words: Biofuel, palm oil, monmorillonite, hydrocracking, catalyst

ABSTRACT
The total palm oil production has increased in the last few years, as a result, palm oil waste which
is a by-product of the milling process will also increase. The palm oil production process in mills
consists of several unit operations. The processing of fresh fruit bunches of palm results in the generation of different types of residue. Among the waste generated, palm oil mill effluent (POME) is
considered as the most harmful waste for the environment if discharged untreated. POME is a thick
brownish liquid that contains high solids, oil and grease. Several treatment technologies have been
used for POME treatment, since the direct discharge of POME adversely affects the environment.
Due to the presence of high oil residue in POME, attempts have been made to recover and convert
it into valuable products such as usefull chemicals and biofuel. Recovery process of oil residue from
POME is difficult and not economical; therefore, its alternative usage is explored. In a preliminary
study, we observed that it was possible to produce various types of liquid hydrocarbons fuel
(biofuel) from oil residue from POME. Oil residue from POME has been catalytically hyrdrocracked
to biofuel by Ni/Mo-ZrO2 pillared monmorillonite catalyst in fixed bed micro reactor. The data show
that the catalytic activity of ZrO2 pillared montmorillonite (ZM) is more active than parent
monmorillonite. While, catalyst Ni/Mo loaded on ZM can increase the catalytic activity for hydrocracking of oil residue from POME into biofuel. The products were mainly gases, biofuel and solid
coke. The biofuel products consist of gasoline, kerosene and diesel oil fraction.
.
INTRODUCTION
Palm oil industry has resulted sludge waste. Palm
oil mill effluent (POME) which contains a significant
amount of oil residue. Oil residues contained in the
palm oil sludge could be potentially processed as an
energy resource. The success of treating palm oil waste
sludge into fuel oil will be significant in resolving the
dependence of fuel oil from fossils and reducing
environmental burdens. Processing of oil residues from
POME into qualified fuel oil can be conducted through
two processes at once, that are process of cracking and
process of hydrogenation or hydrocracking. Hydrocracking oil residues in POME is conducted by
*Corresponding author
Email: ghasanudin@yahoo.co.id

catalytic thermal hydrodecomposition which is able to

alter fat and fatty acids with long carbon chains into
the oil fraction with a shorter hydrocarbon chains and
high potential as a fuel. The study of the conversion of
vegetable oil into fuel is interesting because the materials of vegetable oils do not contain nitrogen, sulfur
and heavy metals so that the resulting oil become an
environmentally friendly oil.
.
Studies on catalytic cracking of vegetables oil into
hydrocarbon fuels have been done, such as Candelilla
oil [1], rapeseed oil [2], palm oil [3,4], soybean oil [5]
and jatropha oil [6]. The result of these studies concluded that the main content of triglyserides in vegetables oil can be converted into hydrocarbon fuel,

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gasoline and diesel fraction. Design of catalyst for

processing vegetable oil from waste sludge of POME
into gasoline fraction is very important and must meet
necessary requirements for its processing. Ni and Mo
metal both in the singular or combination form of both
metals have been investigated as a catalyst for hydrogenation of benzene [7] and hydrocracking of coal
crude oil [8]. The result of these studies concluded
that Ni and Mo metal can be used as a catalyst reaction
for hydrotreatment, hydrocracking and deoxygenation.
Commercial materials which are often used as a hydrogenation catalyst supports and cracking are zeolites, alumina and silica. But these three materials have
small pore radii, making it easy to form coke on the
catalyst surface. In the early twentieth century, it was
introduced cracking catalyst material using acidified
natural clay. However, thermal resistance of clay is not
so high that is not good as catalyst. Monmorillonite
has good nature and chosen as catalytic material because the structure of monmorillonit has high porosity
and surface area; it also has acid site and layer structure which can be swollen. Acid site on monmorillonite can increase porosity of monmorillonite by
pillaring method. In 1977 Brindly introduced metal
oxide pillared clays as catalysts. Metal oxide pillared
clays have some advantages as catalyst supports. Metal
oxides are generally resistant to heat treatment, so that
the metal oxide pillared clays have a high thermal
resistance and can be used as catalyst supports for
high temperature reactions. Metal oxide can be catalysts, so the use of metal oxide has a double function,
as a pillared and as a catalyst agent. Several studies
have included the use of metal oxides ZrO2 as pillared
monmorillonite clay as a catalyst alkylation of benzene [9] and alkylation of phenol [10]. The use of
pillared monmorillonite as catalyst supporting has
sufficient ability to both as catalyst and supporting
.
cracking catalyst [6,8].
Based on the above description, a research of
hydrocracking of oil residue from POME to biofuel
was investigated. The purpose of this research is to
converse oil residue from POME to become a liquid
fuel by using catalyst of nature monmorillonite and
modified pillared ZrO2 monmorillonite (ZM) and
.
Ni/Mo-PM (NMZM).
MATERIALS AND METHODS
1. Oil Residue from POME

The sludge waste (POME) based fatty acid mixture residue was obtained from PT. Sriwijaya Palm Oil
Indonesia-Palembang. It was received as dark brown
pasta, having mild smell, lighter than water and free of
water. The POME was extracted by a soxlet extractor
with gasoline solvent to find the fatty acid mixture. .
2. Catalyst Preparation and Characterization

Natural clay of monmorillonite type was precipitated and dried in oven. It was saturated by using
sodium chloride solution and swirled for 24 h.
Furthermore, the clay was washed by demineralized
water to clean the chloride ion of the clay. This product (Na-monmorillonite) was pillared by zirconium
oxychloride solution. 2 g of montmorillonite was
dispersed into demineralized water and shaken for 5 h.
Zirconium oxychloride was poured into the dispersed
montmorillonite gradually. The result was separated
and washed by demineralized water several times until
it was free of chloride ion. Intercalationed montmorillonite by zircon metal ion was calcinated at temperature of 350 C in O2 atmospher for 4 h, this result is
.
referred as ZrO2 PM.
The ZM was soaked in solution of NiNO3 and
(NH4)6Mo7O24 for 24 h and dried. The ZM containing
Ni and Mo was dried at the temperature of 130 C for
3 h. Then, it was oxidized by flowing O2 gas at the
temperature of 350 C and the flow rate of 1.0 mL s-1
for 3 h. The prepared catalyst was then reduced by
flowing H2 gas at the temperature of 350 C and the
flow rate of 1.0 mL s-1 for 3 h. The product is referred
as NMZM. The BET surface area and pore volume of
the catalyst were measured by nitrogen adsorption
using Autosorb I (Quantachrome Automated Gas
Sorption System). The samples were degassed for 5 h
.
under vacuum at 300 C prior to the analysis.
3. Equipment and Experimental Procedure

The experiments were conducted at atmospheric

pressure in a continuous upflow fixed-bed microreactor. The reactor was a 350 mm long, 35 mm i.d.
stainless steel tube placed in the vertical tube furnace.
The reaction temperature was in 500 C and with a oil
residue feed rate (weight hourly space velocity,
WHSV) of 10 h-1, while the catalyst to oil residue ratio
was 0.2. The catalyst (12 g) with particle size ranged
between 500 and 1000 m was loaded over 1 g of
quartz wool supported with a stainless steel mesh in
the microreactor and the temperature was monitored
by a thermocouple positioned in the center of the
catalyst bed and connected to a temperature controller.
A schematic diagram of the equipment system is
shown in Fig. 1.
.
Hydrogen gas was passed through the reactor for 1
h before the oil recovery from POME was fed using a
peristatic pump. Once steady state had been reached in
the reactor, the liquid product (organic and aqueous
fractions) was collected in a liquid sampler while the
gaseous product was collected in a gas-sampling bulb.
The unconverted fatty acid mixture was separated from
the liquid product in a microdistillation unit operated
at 200 C for 30 min under vacuum. The residue remaining after the vacuum distillation was termed as
the residual fatty acid mixture and the product was
analyzed using gas chromatography.
.

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Hasanudin et al., Sustain. Environ. Res., 22(6), 395-400 (2012)

Temperature
controler

Thermocouple

Condenser

Furnace

Feed

Liquid
Product
Salt Solution
Drain
Peristaltic Pump

Flow meter

H2

Fig. 1. Schematic diagram of the experimental set up.

RESULTS AND DISCUSSION

1. Characterization Oil Residue from POME

2. Result of Preparation and Characterization of

.
Catalyst
.

The result of oil analyst of oil residue from POME

shows that the residue was dominated by a mixture of
free fatty acids of 60-80%. High content of free fatty
acids is adverse because it can cause corrosive to
equipment. So, it is necessary for hydrocracking of
these fatty acids. The the main constituent of fatty
acids from oil residue is shown in Table 1.
.
Table 1. Composition of fatty acids in oil residue from
POME
Fatty acid
Percentage (%)
Caproic acid
1.2
1.5
Caprilic acid
1.5
Myristic acid
63
Palmitic acid
17.4
Oleic acid
7.2
Stearic acid
4.5
Linolenic acid
1.8
Eicosanic acid
1.9
Others

The result of SEM analysis of catalyst montmorillonite, ZM and MNZM at 10.000 times magnification
is shown in Fig. 2. SEM diagrams show no change on
structure and surface texture of nature montmorillonite
and ZM. The comparison between SEM ZM and
NMZM catalyst shows that NMZM catalyst has more
small particles of Ni and Mo metal, attaching on the
surface of ZM. The entrance of Ni and Mo metal to
the surface of ZM does not change the topology of
.
surface of ZM layer.
The XRD data on nature montmorillonite indicates
the characteristic peak at 2 = 5.96 (d = 14.81 ),

Fig. 2. Result of SEM figure of catalyst (a) monmorillonite, (b) ZM and (c) NMZM.

Hasanudin et al., Sustain. Environ. Res., 22(6), 395-400 (2012)

3. Hydrocracking of Oil Residue

Result of hydrocracking oil residue by using catalysts montmorillonite, ZM and NMZM is shown in
Table 3. The data show that catalyst NMZM has the
ability to catalyze hydrocracking process (80% conversion) better than catalysts M and ZM. Although the
presence of zircon, nickel and molybdenum metal in
catalyst can increase the catalytic activity, nickel and
molybdenum also increase the formation of coke on
.
catalysts.
Liquid product is then analized by using gas chromatography to characterize the fraction into gasoline,
Table 3. Result of hydrocracking oil residue
Catalyst
Conversion (%)
Monmorillonite
34
ZM
54
NMZM
85

5.96

M
Intensity

along with other peaks of 2 = 20.10 and 22.11.

Some peaks show another mineral composer that are
characteristic peak of caollinite of 2 = 10.24 (d =
8.63 ) and 18.08 (d = 4.90 ). Overall, diffractogram showed that sample is montmorillonite mineral
.
containing caollinite residue.
The differences between diffractogram of catalyst
of montmorillonite, ZM and NMZM are shown in 2
movement. The emergence of a smaller 2 angle that
is below the peak of 2.5 for the clay showed that the
distance of interlayer of ZM and NMZM catalyst (15
) is greater than the distance of interlayer of montmorillonite catalysts (Fig. 3). This shift indicates a
change in distance between the fields on montmorillonite and ZM, NMZM. On pillared process, pillaring
agent ZrO2 subtituts alkali metal in between monmorillonite layer. Because ZrO2 has a large size molecule
than alkali metal, layer gap of monmorillonite struc.
ture wa increased on ZM and NMZM.
The surface areas and pore volume as calculated
by following BET equations are given in Table 2. The
surface area increased from 25 for montmorillonite
catalyst to 113 for ZM and 74 m2 g-1 for NMZM catalyst. The increased surface area on pillaring is expected, since the process creates regular porosity.
Apparently the ion exchange and subsequent calcinations changed the stacking pattern of the pillared clay.
The total pore volume of the samples is measured by
condensation of N2 adsorbate at P/P0 0.95 in the pores
of diameter < 1400 by the single point method
(Table 2). On pillared technique, the total pore
volume also increased of about 0.0431 mL g-1 in the
monmorillonite to become 0.187 mL g-1 of ZM. The
existing of Ni and Mo metal inside ZM decreased
both specific surface area and pore volume of the catalyst. The phenomenon was caused by Ni and Mo
metals covering the pore and surface of ZM as sup.
porting catalyst.

ZM
NMZM

10
20
Interplanar spacing distance
Fig. 3. XRD paterns of monmorillonite (M), ZM and
NMZM.
Tabel 2. Parameter of catalyst porosity
-1
Catalyst
Surface area (m2 g-1) Volume of pore (mL g )
4.3 x 10-2
Monmorillonite
25
ZM
113
1.9 x 10-1
NMZM
74
1.3 x 10-1

kerosene and diesel with results shown in Fig. 4.

Gasoline product significantly increased from 6% with
montmorillonite catalyst to 16 and 30% when using
ZM and NMZM catalyst, respectively. Ni and Mo
metal on NMZM catalyst facilitated hydrogenation
and cracking reaction to form hydrocarbons.
.
Analysis result showed that the main composition
of oil residue of POME is palmitic acid (C16) which is
fatty acid without double bound and oleic acid (C18)
35
Percentage of product (%)

398

Gasoline
Kerosen
Diesel

30
25
20
15
10
5
0
Monmorillonite

ZM

NMZM

Catalyst

Fig. 4. Anaylisis result of the gasoline, kerosene and

diesel fraction from hydrocracking product.

Organic liquid product (%)

12
32
56

Gas product (%)

15
17
21

Coke (%)
2.8
1.3
6.1

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Hasanudin et al., Sustain. Environ. Res., 22(6), 395-400 (2012)

Layer of monmorillonite

Layer of monmorillonite
-

Si O Si OH Si O Si O Si OH Si O Si O Si OH Si O Si O

Si O Si OH Si O Si O Si OH Si O Si O Si OH Si O Si O

H
O
H 2C
HC
H 2C

O C
O
O C
O
O C

R1

R1

C C C+

C C C

H 2C

Catalytic Cracking HC O

R2

H 2C

Al O Al OH Al O Al O Al OH Al O Al OH Al O Al O
-

C C C

C
O

Hydrogenation

C C C

C
O

R1

R2

Nonene

Ni, Mo

Nonane

Al O Al OH Al O Al O Al OH Al O Al OH Al O Al O

Layer of monmorillonite

Layer of monmorillonite

Fig. 5. Mechanism of catalytic cracking and hydrogenation of triglyceride.

which is fatty acid with one double bound at the middle of carbon chain. First step reaction is cracking of
doble bound carbon chain on oleic acid. Double bound
is easier to be cracked than single bound. One result of
cracking is nonene (C9) with double bound on nonene
reacting with hydrogen forming a more stable molecule nonane. Mechanism of reaction is shown in Fig.
5. However, biofuel products are not only C9, but also
C8, C10, C13, C17 and C19. Before forming light hydrocarbon (C2-C10), triglycerides were firstly cracked because
of thermal cracking of heavy molecule (C12-C20).
.
CONCLUSIONS
Based on the data, we can conclude that pillared
ZM increases porosity of nature monmorilonite,
whereas NMZM decreases the porosity of catalyst.
However, NMZM catalyst can be used as a catalyst for
hydrocracking oil residue from POME with 80% yield
and 30% gasoline fraction. Biofuel product is still a
mixture of gasoline, kerosene and diesel fraction.
Existence of Ni and Mo metal in catalyst is effective
enough to increase biofuel product and gasoline fraction. However, forming of coke during cracking is
unavoidable.
.
ACKNOWLEDGEMENTS
The financial support by the DP2M DIKTI and
Sriwijaya University under STRANAS scheme research grant (No: 0460.a/H9/PL/2010) is gratefully
acknowledged.
.
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Discussions of this paper may appear in the discussion section of a future issue. All discussions should
be submitted to the Editor-in-Chief within six months
of publication.
.
Manuscript Received: July 6, 2012
Revision Received: October 19, 2012
and Accepted: October 30, 2012